Method of controlling undesirable vegetation utilizing certain 3-(substituted thio)-2-benzoyl-cyclohex-2-enones

ABSTRACT

A compound of the formula ##STR1## wherein R is halogen, C 1  -C 2  alkyl, C 1  -C 2  alkoxy, nitro; cyano; C 1  -C 2  haloalkyl, or R a  SO n  - wherein n is 0 or 2 and R a  is C 1  -C 2  alkyl; R 1  is hydrogen or C 1  -C 4  alkyl; R 2  is hydrogen or C 1  -C 4  alkyl; or R 1  and R 2  together are alkylene having 2 to 5 carbon atoms; R 3  is hydrogen or C 1  -C 4  alkyl; R 4  is hydrogen or C 1  -C 4  alkyl; or R 3  and R 4  can be oxo; R 5  is hydrogen or C 1  -C 4  alkyl; R 6  is hydrogen or C 1  -C 4  alkyl; or R 5  and R 6  together are alkylene having 2 to 5 carbon atoms; and R 7  and R 8  independently are (1) hydrogen; (2) halogen; (3) C 1  -C 4  alkyl; (4) C.sub. 1 -C 4  alkoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C 1  -C 4  haloalkyl; (9) R b  SO n  -wherein n is the integer 0, 1 or 2; and R b  is (a) C 1  -C 4  alkyl; (b) C 1  -C 4  alkyl substituted with halogen or cyano; (c) phenyl; or (d) benzyl; (10) --NR c  R d  wherein R c  and R d  independently are hydrogen or C 1  -C 4  alkyl; (11) R e  C(O)- wherein R e  is C 1  -C 4  alkyl or C 1  -C 4  alkoxy; (12) SO 2  NR c  R d  wherein R c  and R d  are as defined; or (13) --N(R c )C(O)R d  wherein R c  and R d  are as defined; m is the integer 0, 1 or 2; and R 9  is C 1  -C 4  alkyl, phenyl, cyano, substituted phenyl, or --(CH 2 ) x  --C(O)O--(C 1  -C 4  alkyl) wherein X is the integer 1, 2 or 3.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a division of application Ser. No. 872,078, filed June 9, 1986, now U.S. Pat. No. 4,762,551.

DESCRIPTION OF THE INVENTION

This invention relates to 3-(substituted thio)-2-benzoyl-cyclohex-2-enones and their use as herbicides.

One embodiment of this invention is an herbicidal composition comprising an herbicidally active 3-(substituted thio)-2-benzoyl-cyclohex-2-enones and an inert carrier therefor wherein the 2-position of the benzoyl moiety is substituted as herein recited and the 4-position preferably is substituted with an electron withdrawing group, such as halogen, cyano or trifluoromethyl. The 4-, 5- and 6-positions of the cyclohex-2-enone moiety can be substituted, preferably with the groups hereinafter recited. More preferably, the cyclohex-2-enone moiety has no substitution or the 4- or 6-position is substituted with two methyl groups. The 3-, 4- and 5-positions of the benzoyl moiety can be substituted, preferably with the groups hereinafter recited.

Also embodied within the scope of this invention are novel compounds having the following structural formula ##STR2## wherein R is halogen; C₁ -C₂ alkyl, preferably methyl; C₁ -C₂ alkoxy, preferably methoxy; nitro; cyano; C₁ -C₂ haloalkyl, preferably trifluoromethyl; or R^(a) SO_(n) -- wherein n is 0 or 2, preferably 2 and R^(a) is C₁ -C₂ alkyl, preferably methyl. Preferably, R is chlorine, bromine, C₁ -C₂ alkyl, C₁ -C₂ alkoxy, cyano, nitro, C₁ -C₂ alkylthio or C₁ -C₂ alkylsulfonyl; more preferably chlorine, nitro, methyl, trifluoromethyl or methylsulfonyl;

R¹ is hydrogen or C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, more preferably methyl, most preferably R¹ is hydrogen or methyl;

R² is hydrogen; C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, more preferably methyl, most preferably R² is hydrogen or methyl; or

R¹ and R² together are alkylene having 2 to 5 carbon atoms;

R³ is hydrogen or C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, more preferably methyl; most preferably R³ is hydrogen or methyl;

R⁴ is hydrogen or C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, more preferably methyl; most preferably R⁴ is hydrogen or methyl; or

R³ and R⁴ together can be oxo;

R⁵ is hydrogen or C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, more preferably methyl; most preferably R⁵ is hydrogen or methyl;

R⁶ is hydrogen or C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, more preferably methyl, most preferably R⁶ is hydrogen; or

R⁵ and R⁶ together are alkylene having 2 to 5 carbon atoms;

R⁷ and R⁸ independently are (1) hydrogen; (2) halogen, preferably chlorine, fluorine or bromine; (3) C₁ -C₄ alkyl, preferably methyl; (4) C₁ -C₄ alkoxy, preferably methoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C₁ -C₄ haloalkyl, more preferably trifluoromethyl; (9) R^(b) SO_(n) -- wherein n is the integer 0, 1 or 2, preferably 2; and

R^(b) is

(a) C₁ -C₄ alkyl, preferably methyl;

(b) C₁ -C₄ alkyl substituted with halogen or cyano, preferably chloromethyl, trifluoromethyl or cyanomethyl;

(c) phenyl; or

(d) benzyl;

(10) --NR^(c) R^(d) wherein

R^(c) and R^(d) independently are hydrogen or C₁ -C₄ alkyl;

(11) R^(e) C(O)-- wherein

R^(e) is C₁ -C₄ alkyl or C₁ -C₄ alkoxy;

(12) --SO₂ NR^(c) R^(d) wherein R^(c) and R^(d) are as defined;

(13) --N(R^(c))C(O)R^(d) wherein R^(c) and R^(d) are as defined; and

m is the integer 0, 1 or 2, preferably 0 or 2, most preferably 2;

R⁹ is C₁ -C₄ alkyl, preferably methyl or ethyl; phenyl; substituted phenyl; cyano; --(CH₂)_(x) C(O)O--(C₁ -C₄ alkyl) wherein x is the integer 1, 2 or 3.

The term "C₁ -C₄ alkyl" includes methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and t-butyl. The term "halogen" includes chlorine, bromine, iodine and fluorine. The term "C₁ -C₄ alkoxy" includes methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy and t-butoxy. The term "C₁ -C₄ haloalkyl" includes the alkyl groups defined above under C₁ -C₄ alkyl in which one or more hydrogen is replaced by chloro, bromo, iodo or fluoro.

Preferably, R⁷ is in the 3-position. Most preferably R⁷ is hydrogen. Preferably R⁸ is in the 4-position. Most preferably R⁸ is halogen, cyano, trifluoromethyl, or R^(b) sO₂ wherein R^(b) is C₁ -C₄ alkyl, preferably methyl or C₁ -C₄ haloalkyl, preferably chloromethyl, difluoromethyl or trifluoromethyl.

The compounds of this invention are active herbicides of a general type. That is, they are herbicidally effective against a wide range of plant species. The method of controlling undesirable vegetation of the present invention comprises applying an herbicidally effective amount of the above-described compounds to the area where control is desired.

The compounds of the present invention can be prepared by the following two- or, if necessary, three-step general method. ##STR3## wherein R through R⁸ are as defined.

Generally in step (a) the benzoyl dione is dissolved in an inert solvent such as methylene dichloride and an excess, usually 150 to 200 mole percent, of oxalyl chloride is added followed by a catalytic amount (0.1 equivalent) of dimethylformamide. The reaction mixture is stirred from one hour to one dayat room temperature. The reaction product is isolated using conventional techniques. ##STR4## wherein R through R⁹ are as defined.

Generally, in step (b) the 3-chloro-2-benzoylcycloalkenone is dissolved in an inert solvent such as tetrahydrofuran and the thiol (1.0 to 2.0 equivalents) is added, followed by a base (1.0 to 2.0 equivalents) such as triethylamine and the solution is stirred 1 to 8 hours at room temperature and the product is isolated using conventional techniques.

Alternatively in step (b), the thiol can be added as a thiolate, preferably the sodium thiolate. The product in step (b) can then be isolated using standard techniques. ##STR5## wherein R through R⁹ are as defined, m is the integer 1 or 2 and [O] is an oxidizing agent, preferably peroxides such as peracetic acid.

Generally, in reaction step (c) the vinylsulfide is dissolved in methylene chloride and an oxidizing agent such as m-chloroperoxybenzoic acid (1.1-2.2 equivalents) is added portion-wise and the reaction stirred for 1 to 8 hours. The product may be isolated using conventional techniques.

The precursor benzoyl diones used in step (a) can be prepared by the following two-step general method.

The process proceeds via the production of an enol ester intermediate as shown in reaction (1). The final product is obtained by rearrangement of the enol ester as shown in reaction (2). The two reactions may be conducted as separate steps by isolation and recovery of the enol ester using conventional techniques prior to conducting step (2), or by addition of a cyanide source to the reaction medium after the formation of the enol ester, or in one step by inclusion of the cyanide source at the start of reaction (1). ##STR6## wherein R through R⁸ are as defined and the moderate base is as defined, preferably tri-C₁ -C₆ alkylamine, alkali metal carbonate or alkali metal phosphate.

Generally, in step (1) mole amounts of the dione and substituted benzoyl reactant are used, along with a mole amount or excess of the base. The two reactants are combined in an organic solvent such as methylene chloride, toluene, ethyl acetate or dimethylformamide. The base or benzoyl reactant preferably is added to the reaction mixture with cooling. The mixture is stirred at 0° C.-50° C. until the reaction is substantially complete.

The reaction product is worked up by conventional techniques. ##STR7##

Generally, in step (2) a mole of the enol ester intermediate is reacted with 1 to 4 moles of the moderate base, preferably about 2 moles of moderate base and from 0.01 mole to about 0.5 mole or higher, preferably about 0.1 mole of the cyanide source (e.g., potassium cyanide or acetone cyanohydrin). The mixture is stirred in a reaction pot until the rearrangement is substantially complete at a temperature below 80° C., preferably about 20° C. to about 40° C., and the desired product is recovered by conventional techniques.

The term "cyanide source" refers to a substance or substances which under the rearrangement conditions consists of or generates hydrogen cyanide and/or cyanide anion.

The process is conducted in the presence of a catalytic amount of a source of cyanide anion and/or hydrogen cyanide, together with a molar excess, with respect to the enol ester, of a moderate base.

Preferred cyanide sources are alkali metal cyanides such as sodium and potassium cyanide; cyanohydrins of methyl alkyl ketones having from 1-4 carbon atoms in the alkyl groups, such as acetone or methyl isobutyl ketone cyanohydrins; cyanohydrins of benzaldehyde or of C₂ -C₅ aliphatic aldehydes such as acetaldehyde, propionaldehyde, etc., cyanohydrins; zinc cyanide; tri(lower alkyl) silyl cyanides, notably trimethyl silyl cyanide; and hydrogen cyanide itself. Hydrogen cyanide is considered most advantageous as it produces relatively rapid reaction and is inexpensive. Among cyanohydrins the preferred cyanide source is acetone cyanohydrin.

The cyanide source is used in an amount up to about 50 mole percent based on the enol ester. It may be used in as littleas about 1 mole percent to produce an acceptable rate of reaction at about 40° C. on a small scale. Larger scale reactions give more reproducible results with slightly higher catalyst levels of about 2 mole percent. Generally about 1-10 mole % of the cyanide source is preferred.

The process is conducted with a molar excess, with respect to the enol ester, of a moderate base. By the term "moderate base" is meant a substance which acts as a base yet whose strength or activity as a base lies between that of strong bases such as hydroxides (which could cause hydrolysis of the enol ester) and that of weak bases such as bicarbonates (which would not function effectively). Moderate bases suitable for use in this embodiment include both organic bases such as tertiary amines and inorganic bases such as alkali metal carbonates and phosphates. Suitable tertiary amines include trialkylamines such as triethylamine. Suitable inorganic bases include potassium carbonate and trisodium phosphate.

The base is used in an amount of from about 1 to about 4 moles per mole of enol ester, preferably about 2 moles per mole.

When the cyanide source is an alkali metal cyanide, particularly potassium cyanide, a phase transfer catalyst may be included in the reaction. Particularly suitable phase transfer catalysts are the Crown ethers.

A number of different solvents are useful in this process, depending on the nature of the acid chloride or the acylated product. A preferred solvent for this reaction is 1,2-dichloroethane. Other solvents which can be employed, depending on the reactants or products include toluene, acetonitrile, methylene chloride, ethyl acetate, dimethylformamide, and methyl isobutyl ketone (MIBK).

In general, depending on the nature of the reactants and the cyanide source, the rearrangment may be conducted at temperatures up to about 50° C.

The above described substituted benzoyl chlorides can be prepared from the corresponding substituted benzoic acids according to the teaching of Reagents for Organic Synthesis, Vol. I, L. F. Fieser and M. Fieser, pp. 767-769 (1967). ##STR8## wherein R, R⁷ and R⁸ are as previously defined.

The substituted benzoic acids can be prepared by a wide variety of general methods according to the teaching of The Chemistry of Carboxylic Acids and Esters, S. Patai, editor, J. Wiley and Sons, New York, N.Y. (1969) and Survey of Organic Synthesis, C. A. Buehler and D. F. Pearson, J. Wiley and Sons, (1970).

The following are four representative examples of the methods described therein. ##STR9## wherein R, R⁷ and R⁸ are as previously defined.

In reaction (a) the substituted benzonitrile is heated to reflux in aqueous sulfuric acid for several hours. The mixture is cooled and the reaction product is isolated by conventional techniques. ##STR10## wherein R, R⁷ and R⁸ are as previously defined.

In reaction (b) the substituted acetophenone is heated to reflux for several hours in an aqueous hypochlorite solution. The mixture is cooled and the reaction product is isolated by conventional techniques. ##STR11## wherein R, R⁷ and R⁸ are as defined and X is chlorine, bromine or iodine.

The substituted aromatic halide is allowed to react with magnesium in a solvent such as ether. The solution is then poured over crushed dry ice and the benzoic acid is isolated by conventional techniques.

The following examples teach the synthesis of a representative compound of this invention.

EXAMPLE I 2-(2-Chloro-4-methanesulfonylbenzoyl)-cyclohexane-1,3-dione ##STR12##

1,3-Cyclohexanedione [11.2 grams (g), 0.1 mole] and 23.3 g (0.1 mole) 2-chloro-4-methanesulfonylbenzoyl chloride were dissolved in 200 ml methylene chloride at room temperature. Triethylamine (11 g, 0.11 mole) was slowly added with cooling. The reaction mixture was stirred at room temperature for 5 hours and then poured into 2N hydrochloric acid. The aqueous phase was discarded and the organic phase dried with MgSO₄ and then evaporated to yield the intermediate enol ester 3-(2-chloro-4-methanesulfonylbenzoyloxy)cyclohex-2-enone. The 3-(2-chloro-4-methanesulfonylbenzoyloxy)cyclohex-2-enone was dissolved in 200 ml acetonitrile and triethylamine (22 g, 0.22 mole) was added all at once, followed by acetonecyanohydrin (0.8 g, 0.01 mole). The solution was stirred for 5 hours and then poured into 2N HCl and extracted twice with ethyl acetate. The organic layer was dried with MgSO₄ and the solvent evaporated to yield the product.

EXAMPLE II 3-Chloro-2-(2-chloro-4-methanesulfonylbenzoyl)-cyclohex-2-enone ##STR13##

2-(2-Chloro-4-methanesulfonylbenzoyl)-cyclohexane-1,3-dione (9.8 g, 30 millimole) was dissolved in 100 ml methylene chloride and stirred at room temperature. To this solution was added oxalyl chloride (5.7 g, 45 mmol) followed by dimethylformamide (0.5 ml) in portions small enough to control effervescence. The resulting solution was stirred for 4 hours and then poured into water and extracted with methylene chloride. The organic layer was washed again with water, saturated K₂ CO₃ solution and then dried with MgSO₄ and the solvent evaporated to yield 3-chloro-2-(2chloro-4-methanesulfonylbenzoyl)cyclohex-2-enone (7.3 g, 70%) as an oil which was used without further purification.

EXAMPLE III 3-Thioethyl-2-(2-chloro-4-methanesulfonylbenzoyl)-cyclohex-2-enone ##STR14##

3-Chloro-2-(2-chloro-4-methanesulfonylbenzoyl)cyclohex-2-enone (4.2 g, 12 mmole) was dissolved in 80 ml THF and ethane thiol (0.75 g, 12 mmole) and triethylamine (1.2 g, 12 mmol) were added and the solution stirred for 18 hours. The reaction mixture was poured into water and extracted with ethyl acetate. The organic layer was washed with 1N HCl, 1N NaOH, water, dried with MgSO₄ and then evaporated to yield 2.9 g (65%) of a rust colored solid, m.p. 151°-154° C.

EXAMPLE IV ##STR15## 3-Ethanesulfonyl-2-(2-chloro-4-methanesulfonylbenzoyl)cyclohex2-enone

3-Thioethyl-2-(2-chloro-4-methanesulfonylbenzoyl)-cyclohex-2-enone (2.0 g, 5.4 mmol) was dissolved in 50 ml methylene chloride and cooled to 0° C. m-Chloroperoxybenzoic acid (2.2 g, 10 mmol @ 80%) was added portion-wise and then stirred for several hours. When TLC showed the reaction was complete, the reaction mixture was transferred to a separatory funnel, more CH₂ Cl₂ was added and the mixture shaken with Na₂ S₂ O₅ solution, and then 5% K₂ CO₃. The organic layer was dried with MgSO₄ and the solvent evaporated to afford 1.1 g of a solid, m.p. 157°-161° C.

The following is a table of certain selected compounds that are preparable according to the procedure described herein. Compound numbers are assigned to each compound and are used throughout the remainder of the application.

                                      TABLE I                                      __________________________________________________________________________      ##STR16##                                                                     Cmpd.                                       m.p.                               No. R  R.sup.1                                                                           R.sup.2                                                                           R.sup.3                                                                          R.sup.4                                                                          R.sup.5                                                                          R.sup.6                                                                          R.sup.7                                                                             R.sup.8                                                                              m R.sup.9   °C.                         __________________________________________________________________________     1   Cl H  H  H H H H 3-Cl 4-Cl  0 C.sub.2 H.sub.5 OC(O)CH.sub.2                                                            55-58                              2   Cl H  H  H H H H 3-Cl 4-Cl  0 phenyl    oil                                3   Cl H  H  H H H H H    4-Cl  0 CH.sub.3  oil                                4   Cl H  H  H H H H H    4-Cl  2 CH.sub.3  oil                                5   NO.sub.2                                                                          CH.sub. 3                                                                         CH.sub.3                                                                          H H H H H    H     2 C.sub.2 H.sub.5                                                                          142-147                            6.sup.a                                                                            Cl H  H  H H H H H    4-SO.sub.2 CH.sub.3                                                                  2 C.sub.2 H.sub.5                                                                          157-161                            7   Cl H  H  H H H H H    4-SO.sub.2 CH.sub.3                                                                  2 CH.sub.3  81-86                              8   NO.sub.2                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H H H H H    H     0 CH.sub.3 OC(O)CH.sub.2                       9   Cl H  H  H H H H H    4-Cl  0 CH.sub.3 OC(O)CH.sub.2                                                                   oil                                10  Cl H  H  H H H H 3-Cl 4-Cl  0 CH.sub.3 OC(O)CH.sub.2                                                                   oil                                11  Cl H  H  H H H H H    4-SO.sub.2 CH.sub.3                                                                  0 CH.sub.3 OC(O)CH.sub.2                                                                   oil                                12  NO.sub.2                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H H H H H    H     2 CH.sub.3                                     13  NO.sub.2                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H H H H H    H     2 CH.sub.3 OC(O)CH.sub.2                                                                   119-124                            14  Cl H  H  H H H H H    4-SO.sub.2 CH.sub.3                                                                  0 CN        123-126                            15  NO.sub.2                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H H H H H    H     0 2,3-dichlorophenyl                                                                       121-125                            16  Cl H  H  H H H H H    4-SO.sub.2 CH.sub.3                                                                  0 4-methoxyphenyl                                                                          oil                                17  Cl H  H  H H H H H    4-SO.sub.2 CH.sub.3                                                                  0 phenyl    186-188                            18  Cl H  H  H H H H H    4-Cl  0 phenyl    oil                                19  Cl H  H  H H H H H    4-Cl  2 phenyl    oil                                20  Cl H  H  H H H H H    4-SO.sub.2 CH.sub.3                                                                  0 3-methylphenyl                                                                           oil                                21  NO.sub.2                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H H H H H    H     0 phenyl    152-156                            23  Cl H  H  H H H H H    4-SO.sub.2 CH.sub.3                                                                  0 2,3-dichlorophenyl                                                                       165-169                            24  Cl H  H  H H H H H    4-SO.sub.2 CH.sub.3                                                                  2 3-methylphenyl                                                                           oil                                25  Cl H  H  H H H H H    4-SO.sub.2 CH.sub.3                                                                  2 4-methoxyphenyl                                                                           99-109                            26  Cl H  H  H H H H H    4-Cl  0 3-methylphenyl                                                                           oil                                27  NO.sub.2                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H H H H H    H     2 2,3-dichlorophenyl                                                                       75-76                              28  NO.sub.2                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H H H H H    H     2 phenyl    oil                                29  Cl H  H  H H H H 3-OC.sub.2 H.sub.5                                                                  4-SO.sub.2 C.sub.2 H.sub.5                                                           0 CH.sub.3  oil                                30  Cl H  H  H H H H H    4-SO.sub.2 CH.sub.3                                                                  1 2,3-dichlorophenyl                                                                        97-102                            31  NO.sub.2                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H H H H H    H     1 3-methyphenyl                                                                            oil                                32  Cl H  H  H H H H H    4-Cl  2 2,3-dichlorophenyl                                                                       161-164                            33  Cl H  H  H H H H 3-Cl 4-Cl  0 3-methylphenyl                                                                           oil                                34  Cl H  H  H H H H 3-Cl 4-Cl  0 phenyl    oil                                35  Cl H  H  H H H H H    4-Cl  0 4-methoxyphenyl                                                                          oil                                36  Cl H  H  H H H H H    4-Cl  2 4-methoxyphenyl                                                                          oil                                37  Cl H  H  H H H H 3-Cl 4-Cl  2 phenyl    69-74                              38  Cl H  H  H H H H 3-C.sub.2 H.sub.5 O                                                                 4-SO.sub.2 C.sub.2 H.sub.5                                                           2 CH.sub.3  60-63                              __________________________________________________________________________      .sup.a = Prepared in Example IV.                                         

Herbicidal Screening Tests

As previously mentioned, the herein described compounds produced in the above-described manner are phytotoxic compounds which are useful and valuable in controlling various plant species. Selected compounds of this invention were tested as herbicides in the following manner.

Pre-Emergence Herbicide Test

On the day preceding treatment, seeds of seven different weed species are planted in loamy sand soil in individual rows using one species per row across the width of a flat. The weeds used are green foxtail (FT) (Setaria viridis), watergrass (WG) (Echinochloa crusgalli), wild oat (WO) (Avena fatua), annula morningglory (AMG) (Ipomoea lacunosa), velvetleaf (VL) (Abutilon theophrasti), Indian mustard (MD) (Brassica juncea) and yellow nutsedge (YNS) (Cyperus esculentus). Ample seeds are planted to give about 20 to 40 seedlings per row, after emergence, depending upon the size of the plants.

Using an analytical balance, 600 milligrams (mg) of the compound to be tested are weighed out on a piece of glassine weighing paper. The paper and compound are placed in a 60 milliliter (ml) wide-mouth clear bottle and dissolved in 45 ml of acetone or substituted solvent. Eighteen ml of this solution are transferred to a 60 ml wide-mouth clear bottle and diluted with 22 ml of a water and acetone mixture (19:1) containing enough polyoxyethylene sorbitan monolaurate emulsifier to give a final solution of 0.5% (v/v). The solution is then sprayed on a seeded flat on a linear spray table calibrated to deliver 80 gallons per acre (748 L/ha). The application rate is 4 lb/acre (4.48 Kg/ha).

After treatment, the flats are placed in the greenhouse at a temperature of 70° to 80° F. and watered by sprinkling. Two weeks after treatment, the degree of injury or control is determined by comparison with untreated check plants of the same age. The injury rating from 0 to 100% is recorded for each species as percent control with 0% representing no injury and 100% representing complete control.

The results of the tests are shown in the following Table II.

                  TABLE II                                                         ______________________________________                                         Pre-Emergence Herbicidal Activity                                              Application Rate -- 4.48 kg/ha                                                 Cmpd.                                                                          No.   FT     WG      WO    AMG   VL    MD    YNS                               ______________________________________                                         1     0      0       0     0     0     0     0                                 2     15     45      0     0     50    30    0                                 3     60     40      0     0     50    50    40                                4     98     100     0     40    100   100   80                                5     100    85      100   20    100   100   80                                6     100    100     90    100   100   100   80                                7     100    100     90    95    100   100   80                                8     100    100     70    30    100   90    70                                9     0      10      0     5     100   100   10                                10    0      10      0     0     100   100   70                                11    0      0       0     0     0     0     0                                 12    100    100     70    10    100   95    80                                13    98     98      50    90    100   80    70                                14    50     100     0     25    100   100   80                                15    0      0       10    0     0     0     0                                 16    0      10      80    95    100   80    80                                17    10     5       90    100   95    80    80                                18    0      0       0     0     0     0     0                                 19    80     5       90    100   100   50    80                                20    0      0       80    50    90    10    80                                21    0      0       0     0     0     0     0                                 22    0      0       0     0     0     0     0                                 23                                                                             24    100    30      100   100   100   40    80                                25    85     10      100   100   90    50    80                                26    0      0       20    20    0     0     10                                27    100    95      100   95    100   30    80                                28    100    95      100   90    100   10    80                                29    100    80      100   100   100   90    80                                30    100    80      100   100   100   80    80                                31    100    100     100   100   100   20    80                                32    0      0       10    10    0     0     30                                33    50     0       10    10    0     0     0                                 34    0      0       10    0     0     0     0                                 35    50     0       80    100   100   0     80                                36    0      0       70    100   100   5     80                                37    0      0       30    100   90    5     0                                 38    100    100     100   100   100   100   80                                ______________________________________                                    

Post-Emergence Herbicide Test

This test is conducted in an identical manner to the testing procedure for the pre-emergence herbicide test, except the seeds of the seven different weed species are planted 10-12 days before treatment. Also, watering of the treated flats is confined to the soil surface and not to the foliage of the sprouted plants.

The results of the post-emergence herbicide test are reported in Table III.

                  TABLE III                                                        ______________________________________                                         Post-Emergence Herbicidal Activity                                             Application Rate - 4.48 kg/ha                                                  Cmpd.                                                                          No.   FT     WG      WO    AMG   VL    MD    YNS                               ______________________________________                                         1     40     60      10    15    60    60    50                                2     10     50      0     30    90    100   0                                 3     60     40      0     0     50    50    40                                4     0      40      0     40    80    50    5                                 5     75     70      70    60    60    40    80                                6     100    100     95    100   100   100   80                                7     90     85      95    80    95    95    60                                8     98     80      80    60    80    75    70                                9     90     100     90    80    100   85    10                                10    85     95      0     70    100   90    10                                11    0      0       0     0     0     0     0                                 12    90     60      50    40    80    60    80                                13    90     80      80    40    100   90    70                                14    10     50      10    40    80    70    10                                15    80     20      80    20    90    20    5                                 16    90     80      100   90    100   100   80                                17    30     30      100   90    100   100   60                                18    10     0       90    80    100   100   5                                 19    70     5       100   100   100   100   80                                20    5      10      95    100   100   100   70                                21    0      20      60    20    80    20    0                                 22    10     20      70    50    50    20    0                                 23                                                                             24    95     85      90    100   100   85    80                                25    100    80      100   100   100   100   80                                26    10     0       90    100   100   75    30                                27    90     80      80    80    90    75    80                                28    90     80      85    80    100   50    80                                29    100    70      100   90    90    90    80                                30    100    90      95    100   100   90    80                                31    100    90      90    100   100   80    80                                32    0      0       80    100   100   50    70                                33    0      0       20    80    100   50    10                                34    0      0       50    100   100   40    5                                 35    10     0       85    100   100   100   30                                36    0      0       70    100   90    20    30                                37    0      0       30    80    80    50    10                                38    80     50      50    80    70    20    80                                ______________________________________                                    

The compounds of the present invention are useful as herbicides and can be applied in a variety of ways at various concentrations. In practice, the compounds herein defined are formulated into herbicidal compositions, by admixture, in herbicidally effective amounts, with the adjuvants and carriers normally employed for facilitating the dispersion of active ingredients for agricultural applications, recognizing the fact that the formulation and mode of application of a toxicant may affect the activity of the materials in a given application. Thus, these active herbicidal compounds may be formulated as granules of relatively large particle size, as wettable powders, as emulsifiable concentrates, as powdery dusts, as flowables, as solutions or as any of several other known types of formulations, depending upon the desired mode of application. These formulations may contain as little as about 0.5% to as much as about 95% or more by weight of active ingredient. A herbicidally effective amount depends upon the nature of the seeds or plants to be controlled and the rate of application varies from about 0.01 to approximately 10 pounds per acre, preferably from about 0.02 to about 4 pounds per acre.

Wettable powders are in the form of finely divided particles which disperse readily in water or other dispersants. The wettable powder is ultimately applied to the soil either as a dry dust or as a dispersion in water or other liquid. Typical carriers for wettable powders include fuller's earth, kaolin clays, silicas and other readily wet organic or inorganic diluents. Wettable powders normally are prepared to contain about 5% to about 95% of the active ingredient and usually also contain a small amount of wetting, dispersing, or emulsifying agent to facilitate wetting and dispersion.

Emulsifiable concentrates are homogeneous liquid compositions which are dispersible in water or other dispersant, and may consist entirely of the active compound with a liquid or solid emulsifying agent, or may also contain a liquid carrier, such as xylene, heavy aromatic naphthal, isophorone and other non-volatile organic solvents. For herbicidal application, these concentrates are dispersed in water or other liquid carrier and normally applied as a spray to the urea to be treated. The percentage by weight of the essential active ingredient may vary according to the manner in which the composition is to be applied, but in comprises about 0.5% to 95% of active ingredient by weight of the herbicidal composition.

Granular formulations wherein the toxicant is carried on relatively coarse particles, are usually applied without dilution to the area in which suppression of vegetation is desired. Typical carriers for granular formulations include sand, fuller's earth, attapulgite clay, bentonite clays, montmorillonite clay, vermiculite, perlite and other organic or inorganic materials which absorb or which may be coated with the toxicant. Granular formulations normally are prepared to contain about 5% to about 25% of active ingredients which may include surface-active agents such heavy aromatic naphthas, kerosene or other petroleum fractions, or vegetable oils; and/or stickers such as destrins, glue or synthetic resins.

Typical wetting, dispersing or emulsifying agents used in agricultural formulations include, for example, the alkyl and alkylaryl sulfonates and sulfates and their salts; polyhydric alcohols; polyethoxylated alcohols; esters and fatty amines; and other types of surface-active agents, many of which are available in commerce. The surface-active agent, when used, normally comprises from 0.1% to 15% by weight of the herbicidal composition.

Dusts, which are free-flowing admixtures of the active ingredient with finely divided solids such as talc, clays, flours and other organic and inorganic solids which act as dispersants and carriers for the toxicant, are useful formulations for soil-incorporating application.

Pastes, which are homogeneous suspensions of a finely divided solid toxicant in a liquid carrier such as water or oil, are employed for specific purposes. These formulations normally contain about 5% to about 95% of active ingredient by weight, and may also contain small amounts of a wetting, dispersing or emulsifying agent to facilitate dispersion. For application, the pastes are normally diluted and applied as a spray to the area to be affected.

Other useful formulations for herbicidal applications include simple solutions of the active ingredient in a dispersant in which it is completely soluble at the desired concentration, such as acetone, alkylated naphthalenes, xylene and other organic solvents. Pressurized sprays, typically aerosols, wherein the active ingredient is dispersed in finely-divided form as a result of vaporization of a low boiling dispersant solvent carrier, such as the Freons, may also be used.

The phytotoxic compositions of this invention can be applied to the plants in the conventional manner. Thus, the dust and liquid compositions can be applied to the plant by the use of power-dusters, boom and hand sprayers and spray dusters. The compositions can also be applied from air planes as a dust or a spray or by rope wick applications because they are effective in very low dosages. In order to modify or control growth of germinating seeds or emerging seedlings, as a typical example, the dust and liquid compositions can be applied to the soil according to conventional methods and can be distributed in the soil to a depth of at least 1/2 inch below the soil surface. It is not necessary that the phytotoxic compositions be mechanically admixed with the soil particles since these compositions can also be applied merely by spraying or sprinkling the surface of the soil. The phytotoxic compositions of this invention can also be applied by addition to irrigation water supplied to the field to be treated. This method of application permits the penetration of the compositions into the soil as the water is absorbed therein. Dust compositions, granular compositions or liquid formulations applied to the surface of the soil can be distributed below the surface of the soil by conventional means such as discing, dragging or mixing operations.

    __________________________________________________________________________     General Formula with Ranges                                                                         Specific Formula                                          __________________________________________________________________________     EMULSIFIABLE CONCENTRATE FORMULATIONS                                          Herbicidal compound                                                                           5-55  herbicidal compound                                                                         24                                           surfactant(s)  5-25  proprietary blend of oil-                                                                   10                                           solvent(s)     20-90 soluble sulfonates and                                                   100%  polyoxyethlene ethers                                                          polar solvent                                                                               27                                                                petroleum hydrocarbon                                                                       39                                                                             100%                                         WETTABLE POWDER FORMULATIONS                                                   herbicidal compound                                                                           3-90  herbicidal compound                                                                         80                                           wetting agent  0.5-2 sodium dialkyl naphthalene                                                                  0.5                                          dispersing agent                                                                              1-8   sulfonate                                                 diluent(s)     8.5-87                                                                               sodium lignosulfonate                                                                       7                                                           100%  attapulgite clay                                                                            12.5                                                                           100%                                         EXTRUDED GRANULAR FORMULATIONS                                                 herbicidal compound                                                                           1-20  herbicidal compound                                                                         10                                           binding agent  0-10  lignin sulonate                                                                             5                                            diluent(s)     70-99 calcium carbonate                                                                           85                                                          100%               100% -                                       FLOWABLE FORMULATIONS                                                          herbicidal compound                                                                           20-70 herbicidal compound                                                                         45                                           surfactant(s)  1-10  polyoxyethylene ether                                                                       5                                            suspending agent(s)                                                                           0.05-1                                                                               attagel      0.05                                         antifreeze agent                                                                              1-10  propylene glycol                                                                            10                                           antimicrobial agent                                                                           1-10  1,2-benzisothiazoline-3-one                                                                 0.03                                         antifoam agent 0.1-1 silicone defoamer                                                                           0.02                                         solvent        7.95-77.85                                                                           water        39.9                                                        100%               100%                                         __________________________________________________________________________

The phytotoxic compositions of this invention can also contain other additives, for example, fertilizers, other herbicides and other pesticides, used as adjuvant or in combination with any of the above-described adjuvants. Fertilizers useful in combination with the active ingredients include, for example, ammonium nitrate, urea and superphosphate. 

What is claimed is:
 1. The method of controlling undesirable vegetation comprising applying to the area where control is desired, an herbicidally effective amount of a compound having the formula ##STR17## wherein R is halogen, C₁ -C₂ alkyl, C₁ -C₂ alkoxy, nitro; cyano; C₁ -C₂ haloalkyl, or R^(a) SO_(n) -- wherein n is 0 or 2 and R^(a) is C₁ -C₂ alkyl;R¹ is hydrogen or C₁ -C₄ alkyl; R² is hydrogen or C₁ -C₄ alkyl; or R¹ and R² together are alkylene having 2 to 5 carbon atoms; R³ is hydrogen or C₁ -C₄ alkyl; R⁴ is hydrogen or C₁ -C₄ alkyl; or R³ and R⁴ together can be oxo; R⁵ is hydrogen or C₁ -C₄ alkyl; R⁶ is hydrogen or C₁ -C₄ alkyl; or R⁵ and R⁶ together are alkylene having 2 to 5 carbon atoms; R⁷ and R⁸ independenntly are (1) hydrogen; (2) halogen; (3) C₁ -C₄ alkyl; (4) C₁ -C₄ alkoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C₁ -C₄ haloalkyl; (9) R^(b) SO_(n) -- wherein n is the integer 0, 1 or 2; and R^(b) is (a) C₁ -C₄ alkyl; (b) C₁ -C₄ alkyl substituted with halogen or cyano; (c) phenyl; or (d) benzyl; (10) --NR^(c) R^(d) wherein R^(c) and R^(d) independently are hydrogen or C₁ -C₄ alkyl; (11) R^(e) C(O)-- wherein R^(e) is C₁ -C₄ alkyl or C₁ -C₄ alkoxy; (12) SO₂ NR^(c) R^(d) wherein R^(c) and R^(d) are as defined; or (13) --N(R^(c))C(O)R^(d) wherein R^(c) and R^(d) are as defined; and m is the integer 0, 1 or 2; and R⁹ is C₁ -C₄ alkyl, phenyl, dichlorophenyl; methylphenyl; methoxyphenyl; cyano, or --(CH₂)_(x) C(O)O--(C₁ -C₄ alkyl) wherein X is the integer 1, 2 or
 3. 2. The method of claim 1 wherein R is chlorine, bromine, C₁ -C₂ alkyl, C₁ -C₂ alkoxy, cyano, nitro, C₁ -C₂ alkylthio or C₁ -C₂ alkylsulfonyl; R¹ is hydrogen or methyl; R² is hydrogen or methyl; R³ is hydrogen or methyl; R⁴ is hydrogen or methyl; R⁵ is hydrogen or methyl; R⁶ is hydrogen or methyl; R⁷ and R⁸ independently are (1) hydrogen; (2) halogen; (3) C₁ -C₄ alkyl; (4) C₁ -C₄ alkoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C₁ -C₄ haloalkyl; (9) R^(b) SO_(n) -- wherein n is the integer 0, 1 or 2; and R^(b) is (a) C₁ -C₄ alkyl; (b) C₁ -C₄ alkyl substituted wit halogen or cyano; (c) phenyl; or (d) benzyl; (10) --NR^(c) R^(d) wherein R^(c) and R^(d) independently are hydrogen or C₁ -C₄ alkyl; (11) R^(e) C(O)-- wherein R^(e) is C₁ -C₄ alkyl or C₁ -C₄ alkoxy; (12) SO₂ NR^(c) R^(d) wherein R^(c) and R^(d) are as defined; or (13) --N(R^(c))C(O)R^(d) wherein R^(c) and R^(d) are as defined; m is 0, 1 or 2; and R⁹ is methyl, ethyl, phenyl, CH₃ OC(O)CH₂ --, C₂ H₅ OC(O)CH₂, dichlorophenyl, methylphenyl, methoxyphenyl or cyano.
 3. The method of claim 2 wherein R⁷ and R⁸ are independently are hydrogen; chlorine; fluorine; bromine; methyl; methoxy; trifluoromethoxy; cyano; nitro; trifluoromethyl; R^(b) SO_(n) -- wherein n is the integer 2 and R^(b) is methyl, chloromethyl, trifluoromethyl, cyanomethyl, ethyl, or n-propyl; --NR^(c) R^(d) wherein R^(c) and R^(d) independently are hydrogen or C₁ -C₄ alkyl; R^(e) C(O)-- where R^(e) is C₁ -C₄ alkyl or C₁ -C₄ alkoxy or SO₂ NR^(c) R^(d) wherein R^(c) and R^(d) are as defined and R⁷ is in the 3-position, and R⁸ is in the 4-position.
 4. The method of claim 2 wherein R⁷ is hydrogen; R⁸ is hydrogen; chlorine; bromine; fluorine; trifluoromethyl; or R² SO₂ wherein R^(b) is C₁ -C₄ alkyl; and R⁹ is methyl, ethyl or phenyl.
 5. The method of claim 2 wherein R is chlorine; R¹ is hydrogen; R² is hydrogen; R³ is hydrogen; R⁴ is hydrogen; R⁵ is hydrogen; R⁶ is hydrogen; R⁷ is hydrogen; R⁸ is 4--CH₃ SO₂ ; R⁹ is ethyl; and m is
 2. 6. The method of claim 2 wherein R is chlorine; R¹ is hydrogen; R² is hydrogen; R³ is hydrogen; R⁴ is hydrogen; R⁵ is hydrogen; R⁶ is hydrogen; R⁷ is hydrogen; R⁸ is 4--CH₃ SO₂ --; R⁹ is methyl; and m is
 2. 7. The method of claim 2 wherein R is nitro; R¹ is methyl; R² is methyl; R³ is hydrogen; R⁴ is hydrogen; R⁵ is hydrogen; R⁶ is hydrogen; R⁷ is hydrogen; R⁸ is hydrogen; R⁹ is phenyl; and m is
 0. 8. The method of claim 2 wherein R is chlorine; R¹ is hydrogen; R² is hydrogen; R³ is hydrogen; R⁴ is hydrogen; R⁵ is hydrogen; R⁶ is hydrogen; R⁷ is hydrogen; R⁸ is 4--CH₃ SO₂ --; R⁹ is 2,3-dichlorophenyl; and m is is
 1. 9. The method of claim 2 wherein R is nitro; R¹ is methyl; R² is methyl; R³ is hydrogen; R⁴ is hydrogen; R⁵ is hydrogen; R⁶ is hydrogen; R⁷ is hydrogen; R⁸ is hydrogen; R⁹ is 3-methylphenyl; and m is
 1. 10. The method of claim 2 wherein R is chlorine; R¹ is hydrogen; R² is hydrogen; R³ is hydrogen; R⁴ is hydrogen; R⁵ is hydrogen; R⁶ is hydrogen; R⁷ is 3-ethoxy; R⁸ is 4--C₂ H₅ SO₂ --; R⁹ is methyl; and m is
 2. 